Highly effective long-acting antibacterial polyester composite material and preparation method thereof

Abstract

This application relates to the field of polymer materials technology, specifically disclosing a high-efficiency, long-lasting antibacterial polyester composite material and its preparation method; the high-efficiency, long-lasting antibacterial polyester composite material comprises the following raw materials in parts by weight: 80-95 parts of polyester melt, 0.5-5 parts of composite antibacterial agent, 0.1-1 parts of dispersant, and 0.5-3 parts of interface compatibilizer; the composite antibacterial agent is a complex of nano-zinc dioxide and organic quaternary ammonium salt, wherein the organic quaternary ammonium salt is a double long-chain quaternary ammonium salt; the use of double long-chain quaternary ammonium salt in this application can compensate for the slow onset of action of nano-zinc dioxide, and nano-zinc dioxide can slowly release zinc ions to achieve a long-lasting protective effect. The combination of the two promotes the preparation of polyester material to achieve both good immediate contact sterilization and long-lasting protection.

Description

Technical Field

[0001] This application relates to the field of polymer materials technology, and in particular to a high-efficiency, long-lasting antibacterial polyester composite material and its preparation method. Background Technology

[0002] Polyester materials are widely used in textiles, packaging, electronics, automobiles, and other fields due to their excellent physical properties, chemical stability, and processing performance. However, ordinary polyester materials do not possess antibacterial properties, making them prone to bacterial growth in applications with high hygiene requirements, which can lead to various hygiene problems. This, to some extent, limits the further promotion and application of polyester materials.

[0003] In existing technologies, conventional modification methods that involve adding a single antibacterial agent to impart antibacterial properties to polyester materials often result in low antibacterial efficiency and short antibacterial duration. Furthermore, the poor interfacial compatibility between the antibacterial agent and the polyester matrix, along with uneven dispersion within the matrix, not only further reduces the stability of the antibacterial effect but also easily damages the mechanical properties of the polyester material. This makes it difficult to meet the practical application requirements for polyester materials to achieve efficient, long-lasting antibacterial effects while maintaining good overall performance. Summary of the Invention

[0004] To address the shortcomings of existing polyester materials in terms of antibacterial properties, this application provides a high-efficiency, long-lasting antibacterial polyester composite material and its preparation method.

[0005] In a first aspect, this application provides a high-efficiency, long-lasting antibacterial polyester composite material, which adopts the following technical solution: A high-efficiency, long-lasting antibacterial polyester composite material comprises the following raw materials in parts by weight: 80-95 parts of polyester melt, 0.5-5 parts of composite antibacterial agent, 0.1-1 parts of dispersant, and 0.5-3 parts of interface compatibilizer; wherein the composite antibacterial agent is a composite of nano zinc dioxide and organic quaternary ammonium salt, and the organic quaternary ammonium salt is a double long-chain quaternary ammonium salt.

[0006] By employing the above-mentioned technical solutions, nano-zinc oxide can generate reactive oxygen species through photocatalysis and slowly release zinc ions, thereby disrupting the bacterial cell structure. The dual-chain quaternary ammonium salt can electrostatically adsorb onto the negatively charged bacterial cell membrane, tearing the membrane structure and causing leakage of cell contents. Nano-zinc oxide particles can act as physical anchors, undergoing physical adsorption or weak interactions with organic quaternary ammonium salt molecules during the composite process, helping to slow down the free migration of organic molecules and thus prolonging the antibacterial durability of the polyester material. Compared to conventional organic quaternary ammonium salts, the dual-chain quaternary ammonium salt exhibits stronger lipid solubility, enabling it to more efficiently disrupt the bacterial phospholipid bilayer and improve the bactericidal efficiency of the polyester material. Simultaneously, the combination of the dual-chain quaternary ammonium salt and nano-zinc dioxide allows the dual-chain quaternary ammonium salt to compensate for the slower onset of action of nano-zinc dioxide, while the nano-zinc dioxide slowly releases zinc ions, achieving a long-lasting protective effect. The combination of these two technologies results in a polyester material that achieves both effective immediate contact sterilization and long-lasting protection.

[0007] Preferably, the mass ratio of the nano zinc dioxide to the dual long-chain quaternary ammonium salt is (1-3):1, and the dual long-chain quaternary ammonium salt is bis(decyl)dimethylammonium chloride.

[0008] By adopting the above technical solution and using quaternary ammonium salts with a C10 chain length, better hydrophobicity and bactericidal effect are achieved, which can better compatibility with polyester melt, uniformly disperse antibacterial components in the composite material system, and improve the uniformity and stability of the antibacterial performance of polyester materials.

[0009] Preferably, the nano-zinc dioxide is surface-modified with a silane coupling agent, including the following specific steps: Modified nano zinc dioxide was obtained by mixing nano zinc dioxide with a silane coupling agent in a solvent, ultrasonically dispersing the mixture, and drying it after the reaction.

[0010] By adopting the above technical solution, the modification of nano-zinc dioxide with a silane coupling agent can reduce nanoparticle aggregation and promote the uniform dispersion of nano-zinc dioxide in the composite material system. On the other hand, the modification of nano-zinc dioxide with a silane coupling agent can enhance the interfacial bonding strength between nano-zinc dioxide and polyester melt, reduce the debonding phenomenon between nano-zinc dioxide and polyester matrix, and improve the antibacterial durability and tensile strength of polyester composite materials.

[0011] Preferably, the amount of silane coupling agent used is 1-3% of the mass of nano zinc oxide.

[0012] Preferably, the heating temperature is 75-85℃.

[0013] Preferably, the dispersant is polyethylene glycol stearate, and the interfacial compatibilizer is maleic anhydride-grafted polyester.

[0014] Preferably, the polyester composite material raw material further includes 3-5 parts of polyethylene oxide and 1-3 parts of calcium chloride.

[0015] By adopting the above technical solution, polyethylene oxide and calcium chloride are added to the polyester composite material. Calcium chloride can improve the bactericidal efficiency and speed of quaternary ammonium salts, making it easier for quaternary ammonium salts to be adsorbed onto bacterial cell membranes. At the same time, polyethylene oxide can act as a water-absorbing carrier, preventing calcium chloride particles from agglomerating and preventing the water absorbed by calcium chloride from being lost or migrated too quickly, thereby improving the dispersibility and uniformity of the polyester material system.

[0016] On the other hand, polyethylene oxide and calcium chloride can form a complex that can accelerate the crystallization of polyester melt. At the same time, polyethylene oxide can be used to improve the toughness and heat distortion temperature of polyester materials, thereby further improving the strength and thermal stability of polyester materials.

[0017] Secondly, this application provides a method for preparing a high-efficiency, long-lasting antibacterial polyester composite material, using the following technical solution: A method for preparing a high-efficiency, long-lasting antibacterial polyester composite material includes the following specific steps: The composite antibacterial agent and dispersant are mixed evenly, then mixed with polyester melt and interfacial compatibilizer, heated and stirred, and melt polymerized to obtain a high-efficiency and long-lasting antibacterial polyester composite material.

[0018] By adopting the above technical solution, the composite antibacterial agent is combined with the synergistic effect of each component during the polyester melt polymerization process, which promotes the preparation of polyester composite material to have a long-lasting antibacterial effect while maintaining good mechanical properties.

[0019] Preferably, the heating temperature is 250-280℃.

[0020] Preferably, the composite antibacterial agent and dispersant are mixed evenly, and then mixed with polyethylene oxide, calcium chloride, polyester melt and interface compatibilizer, heated and stirred, and melt polymerized to obtain a high-efficiency and long-lasting antibacterial polyester composite material.

[0021] In summary, this application has the following beneficial effects: 1. Because this application uses a composite of nano-zinc dioxide and organic quaternary ammonium salt as a composite antibacterial agent added to polyester composite materials, it helps to slow down the free migration of organic molecules, thereby prolonging the antibacterial durability of the polyester material. The organic quaternary ammonium salt uses a double long-chain quaternary ammonium salt, which has stronger lipophilicity and can more efficiently destroy the phospholipid bilayer of bacteria, thereby improving the bactericidal efficiency of the polyester material.

[0022] 2. This application uses C10-chain-length didecyl dimethyl ammonium chloride, which has better hydrophobicity and bactericidal effect, improving the uniformity and stability of the antibacterial properties of polyester materials. Adding polyethylene oxide and calcium chloride to the polyester composite material can form a complex, which can accelerate the crystallization of the polyester melt. Simultaneously, polyethylene oxide can improve the toughness and heat distortion temperature of the polyester material, further enhancing its strength and thermal stability. Detailed Implementation

[0023] The present application will be further described in detail below with reference to the embodiments.

[0024] All raw materials used in the examples are commercially available. Example 1

[0025] This embodiment provides a high-efficiency, long-lasting antibacterial polyester composite material, comprising the following raw materials in parts by weight: 87 kg of polyester melt, 3 kg of composite antibacterial agent, 0.5 kg of dispersant, and 2 kg of interface compatibilizer.

[0026] The composite antibacterial agent is a complex of nano-zinc dioxide and organic quaternary ammonium salt, wherein the organic quaternary ammonium salt is a bis(decyl)dimethylammonium chloride, and the mass ratio of nano-zinc dioxide to bis(decyl)dimethylammonium chloride is 2:1; the polyester melt is prepared by esterification reaction of terephthalic acid, ethylene glycol and antimony glycol in a molar ratio of 1.2:1:0.001 at 250℃ for 2 hours; the interface compatibilizer is maleic anhydride-grafted polyester with a grafting rate of 0.8%; and the dispersant is polyethylene glycol stearate.

[0027] The preparation method of high-efficiency and long-lasting antibacterial polyester composite material includes the following specific steps: The composite antibacterial agent and dispersant are mixed evenly, and then mixed with polyester melt and interface compatibilizer. Melt polymerization is carried out at 280℃, vacuum ≤40Pa, and stirring speed 60rpm. When the intrinsic viscosity of the mixture reaches 0.68dl / g, the vacuum is released, nitrogen is filled, and the mixture is discharged and pelletized to obtain a high-efficiency and long-lasting antibacterial polyester composite material.

[0028] Example 2

[0029] The difference between Example 2 and Example 1 is that the high-efficiency long-lasting antibacterial polyester composite material includes the following raw materials in parts by weight: 80 kg of polyester melt, 5 kg of composite antibacterial agent, 0.1 kg of dispersant, and 3 kg of interface compatibilizer.

[0030] Example 3 The difference between Example 3 and Example 1 is that the high-efficiency long-lasting antibacterial polyester composite material includes the following raw materials in parts by weight: 95 kg of polyester melt, 0.5 kg of composite antibacterial agent, 1 kg of dispersant, and 0.5 kg of interface compatibilizer.

[0031] Example 4 The difference between Example 4 and Example 1 is that the mass ratio of nano zinc dioxide and double long-chain quaternary ammonium salt in the composite antibacterial agent is 1:1.

[0032] Example 5 The difference between Example 5 and Example 1 is that the mass ratio of nano zinc dioxide and double long-chain quaternary ammonium salt in the composite antibacterial agent is 3:1.

[0033] Example 6 The difference between Example 6 and Example 1 is that the nano zinc dioxide is surface modified with a silane coupling agent.

[0034] The preparation method of high-efficiency and long-lasting antibacterial polyester composite material includes the following specific steps: S1: Dissolve nano zinc dioxide in ethanol solvent, then add silane coupling agent KH550 and mix. The amount of silane coupling agent is 2% of the mass of nano zinc oxide. Disperse by ultrasonication, heat to 80℃ and react for 2 hours. After centrifugation and drying, obtain modified nano zinc dioxide. Mix the modified nano zinc dioxide with a double long-chain quaternary ammonium salt to prepare a composite antibacterial agent.

[0035] S2: Mix the composite antibacterial agent and dispersant evenly, then mix with polyester melt and interface compatibilizer, and carry out melt polymerization at 280℃, vacuum ≤40Pa, and stirring speed 60rpm. When the intrinsic viscosity of the mixture reaches 0.68dl / g, release the vacuum, purge with nitrogen, discharge and pelletize to obtain a high-efficiency and long-lasting antibacterial polyester composite material.

[0036] Example 7 The difference between Example 7 and Example 6 is that the amount of silane coupling agent used in the modified nano zinc oxide raw material is 1% of the mass of nano zinc oxide.

[0037] Example 8 The difference between Example 8 and Example 6 is that the amount of silane coupling agent used in the modified nano zinc oxide raw material is 3% of the mass of nano zinc oxide.

[0038] Example 9 The difference between Example 9 and Example 6 is that the polyester composite material also includes 4 kg of polyethylene oxide. The relative molecular mass of polyethylene oxide is 1.5 million.

[0039] The preparation method of high-efficiency and long-lasting antibacterial polyester composite material includes the following specific steps: S1: Dissolve nano zinc dioxide in ethanol solvent, then add silane coupling agent KH550 and mix. The amount of silane coupling agent is 2% of the mass of nano zinc oxide. Disperse by ultrasonication, heat to 80℃ and react for 2 hours. After centrifugation and drying, obtain modified nano zinc dioxide. Mix the modified nano zinc dioxide with a double long-chain quaternary ammonium salt to prepare a composite antibacterial agent.

[0040] S2: Mix the composite antibacterial agent and dispersant evenly, then mix with polyester melt, interface compatibilizer and polyethylene oxide, and carry out melt polymerization at 280℃, vacuum ≤40Pa and stirring speed 60rpm. When the intrinsic viscosity of the mixture reaches 0.68dl / g, release the vacuum, purge with nitrogen and granulate to obtain a high-efficiency and long-lasting antibacterial polyester composite material.

[0041] Example 10 The difference between Example 10 and Example 9 is that the polyester composite material raw material also includes 2 kg of calcium chloride.

[0042] The preparation method of high-efficiency and long-lasting antibacterial polyester composite material includes the following specific steps: S1: Dissolve nano zinc dioxide in ethanol solvent, then add silane coupling agent KH550 and mix. The amount of silane coupling agent is 2% of the mass of nano zinc oxide. Disperse by ultrasonication, heat to 80℃ and react for 2 hours. After centrifugation and drying, obtain modified nano zinc dioxide. Mix the modified nano zinc dioxide with a double long-chain quaternary ammonium salt to prepare a composite antibacterial agent.

[0043] S2: Mix the composite antibacterial agent and dispersant evenly, then mix with polyester melt, interface compatibilizer, polyethylene oxide and calcium chloride, and carry out melt polymerization at 280℃, vacuum ≤40Pa and stirring speed 60rpm. When the intrinsic viscosity of the mixture reaches 0.68dl / g, release the vacuum, purge with nitrogen and discharge into pellets to obtain a high-efficiency and long-lasting antibacterial polyester composite material.

[0044] Example 11 The difference between Example 11 and Example 10 is that the amount of polyethylene oxide used in the polyester composite material is 3 kg, and the amount of calcium chloride used is 3 kg.

[0045] Example 12 The difference between Example 12 and Example 10 is that the amount of polyethylene oxide used in the polyester composite material is 5 kg, and the amount of calcium chloride used is 1 kg.

[0046] Comparative Example Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that an equal amount of nano zinc dioxide was used instead of the composite antibacterial agent in the raw material of the high-efficiency long-lasting antibacterial polyester composite material.

[0047] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that an equal amount of double long-chain quaternary ammonium salt was used instead of the composite antibacterial agent in the raw material of the high-efficiency long-lasting antibacterial polyester composite material.

[0048] Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that an equal amount of benzalkonium chloride was used instead of the double long-chain quaternary ammonium salt in the raw material of the high-efficiency long-lasting antibacterial polyester composite material.

[0049] Performance testing The following performance tests were conducted on the high-efficiency, long-lasting antibacterial polyester composite materials provided in Examples 1-12 and Comparative Examples 1-3 of this application. The specific test results are shown in Table 1.

[0050] Detection methods I. Antibacterial properties Referring to the standard GB / T20944-2007 "Evaluation of antimicrobial properties of textiles - Part 2: Absorption method", the test bacteria were Staphylococcus aureus and Escherichia coli. The antimicrobial properties of the high-efficiency long-lasting antimicrobial polyester composite material prepared in this application and the antimicrobial effect after 50 washes were tested.

[0051] II. Mechanical Properties Referring to the standard CB / T1040.1-2018 "Determination of Tensile Properties of Plastics - Part 1", the specimen was dumbbell-shaped with dimensions of 115mm x 10mm x 4mm, the tensile speed was 20mm / min, the initial distance between the clamps was 115mm, and the gauge length was 50mm. The tensile strength of the high-efficiency long-lasting antibacterial polyester composite material prepared in this application was tested. Referring to the standard CB / T1043.1-2008 "Determination of Impact Properties of Simply Supported Beams of Plastics - Part 1", the specimen was 80mm long, 10mm wide, and 4mm thick, with a bending speed of 5mm / min. The bending properties of the high-efficiency long-lasting antibacterial polyester composite material prepared in this application were tested.

[0052] Table 1: Performance Test Results Data Table

[0053] The performance test results show that the high-efficiency long-lasting antibacterial polyester composite material prepared in this application has a long-lasting antibacterial effect. At the same time, under the synergistic effect of various components, it can still maintain good tensile strength and toughness at a high processing temperature.

[0054] A comparison of Comparative Examples 1-3 and Example 1 shows that Comparative Example 1 uses a single nano-zinc dioxide as the antibacterial component, Comparative Example 2 uses a single double long-chain quaternary ammonium salt as the antibacterial component, and Comparative Example 3 uses an equal amount of benzalkonium chloride instead of the double long-chain quaternary ammonium salt. The performance test results show that the antibacterial effect and antibacterial durability of the prepared polyester composite material are reduced. This further illustrates that the present application adds a composite antibacterial agent of nano-zinc dioxide and organic quaternary ammonium salt to the polyester composite material to achieve both immediate contact sterilization and long-term protection.

[0055] As can be seen from Examples 9-12, adding polyethylene oxide and calcium chloride to the polyester composite material system can further improve the antibacterial effect and strength of the polyester material, and promote the maintenance of the antibacterial durability of the antibacterial components at higher heating temperatures.

[0056] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A high-efficiency, long-lasting antibacterial polyester composite material, characterized in that, The raw materials include the following parts by weight: 80-95 parts polyester melt, 0.5-5 parts composite antibacterial agent, 0.1-1 parts dispersant, and 0.5-3 parts interface compatibilizer; wherein the composite antibacterial agent is a composite of nano zinc dioxide and organic quaternary ammonium salt, and the organic quaternary ammonium salt is a double long-chain quaternary ammonium salt.

2. The high-efficiency, long-lasting antibacterial polyester composite material according to claim 1, characterized in that, The mass ratio of the nano zinc dioxide to the dual long-chain quaternary ammonium salt is (1-3):1, and the dual long-chain quaternary ammonium salt is bis(decyl)dimethylammonium chloride.

3. The high-efficiency, long-lasting antibacterial polyester composite material according to claim 1, characterized in that, The nano-zinc dioxide is surface-modified with a silane coupling agent, including the following specific steps: Modified nano zinc dioxide was obtained by mixing nano zinc dioxide with a silane coupling agent in a solvent, ultrasonically dispersing the mixture, heating it to react, and then drying it.

4. The high-efficiency, long-lasting antibacterial polyester composite material according to claim 3, characterized in that, The amount of silane coupling agent used is 1-3% of the mass of nano zinc oxide.

5. The high-efficiency, long-lasting antibacterial polyester composite material according to claim 3, characterized in that, The heating temperature is 75-85℃.

6. The high-efficiency, long-lasting antibacterial polyester composite material according to claim 1, characterized in that, The dispersant is polyethylene glycol stearate, and the interfacial compatibilizer is maleic anhydride-grafted polyester.

7. The high-efficiency, long-lasting antibacterial polyester composite material according to claim 1, characterized in that, The polyester composite material raw materials also include 3-5 parts of polyethylene oxide and 1-3 parts of calcium chloride.

8. A method for preparing a high-efficiency, long-lasting antibacterial polyester composite material as described in any one of claims 1-7, characterized in that, The specific steps include the following: The composite antibacterial agent and dispersant are mixed evenly, then mixed with polyester melt and interfacial compatibilizer, heated and stirred, and melt polymerized to obtain a high-efficiency and long-lasting antibacterial polyester composite material.

9. The method for preparing the high-efficiency long-lasting antibacterial polyester composite material according to claim 8, characterized in that, The heating temperature is 250-280℃.

10. The method for preparing the high-efficiency, long-lasting antibacterial polyester composite material according to claim 8, characterized in that, The composite antibacterial agent and dispersant are mixed evenly, and then mixed with polyethylene oxide, calcium chloride, polyester melt and interface compatibilizer. The mixture is heated and stirred to melt polymerize and obtain a high-efficiency and long-lasting antibacterial polyester composite material.

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